Sheet 1 Surface Chemistry e

Surface Chemistry
INTRODUCTION :
Surface chemistry is that branch of chemistry which deals with study of the phenomena occuring at the
surface or interface, i.e. at the boundary separating two bulk phases. In this chapter our main emphasis will
be on three important topics related to surface chemistry, viz., adsorption, colloids and emulsions.
 Adsorption : The phenomenon of attracting and retaining the molecules of a substance on the surface
of a liquid or a solid resulting into a higher concentration of the molecules on the surface is called adsorption.
As a result of adsorption, there is a decrease of surface energy. The process of removal of an adsorbed
substance from the surface on which it is adsorbed is called desorption. It is the reverse of adsorption and
can be brought about by heating or by reducing the pressure.
Adsorbent and adsorbate :The substance on the surface of which adsorption occurs is known as
adsorbent. The substances that get adsorbed on the solid surface due to intermolecular attractions are
called adsorbate.Charcoal, silica, gel, alumina gel are good adsorbents because they have highly porous
structures and have large surface area. Colloids on account of their extremely small dimensions possess
enoromous surface area per unit mass and are, therefore, also good adsorbents.
Examples of adsorption :
 Adsorption of a gas by charcoal : Finely divided activated charcoal has a tendency to adsorb a number
of gases like ammonia, sulphur dioxide, chlorine, phosgene, etc. In this case, charcoal acts as an adsorbent
while gas molecules act as adsorbate.
 Adsorption of a dye by charcoal : Animal charcoal is used for decolourising a number of organic
substances in the form of their solutions. The discharge of the colour is due to the fact that the coloured
component (generally an organic dye) gets adsorbed on the surface of the adsorbent (animal charcoal).
Sorption : When both adsorption and absorption take place simultaneously.
Eg : Dyes get adsorbed as well as absorbed in the cotton fibre i.e. sorption takes place.
Difference between adsorption and absorption :
The terms adsorption and absorption are different. Adsorption is a phenomenon in which there is higher
concentration of another substance on the surface than in the bulk. On the other hand, absorption is a
phenomenon in which the molecules of a substance are uniformly distributed throughout the body of other
substance. For example, when silica gel is placed in the environment of water, it adsorbs the water vapour.
The water vapour are present in high concentration at the surface of silica gel. On the other hand, when
calcium chloride is placed in the environment of water, it absorbs water. The water vapour uniformly get
distributed throughout the body of calcium chloride. Thus, silica gel adsorbs water vapour while anhydrous
calcium chloride absorbs water.
 Thermodynamics of adsorption : Adsorption is an exothermic process. Therefore H of adsorption is
always negative. When a gas is adsorbed the entropy of the gas decreases i.e. S is negative. Adsorption is
thus accompanied by decrease in enthalpy as well as entropy of the system, for a process to be spontaneous
requirement is that G must be negative. On the basis of equation, G = H - TS, G can be negative if H
has sufficiently high negative value as - TS is positive. Thus, in an adsorption process, which is spontaneous,
S is negative, and H is also sufficiently negative and as a combination of these two factors, G is negative.
H becomes less and less negative as adsorption proceeds further and further. Ultimately H becomes
equal to TS and G becomes zero. This is the state at which equilibrium is attained.
 Enthalpy of adsorption Hadsorption : It is the amount of the heat released when 1 mole of an adsorbate
gets adsorbed on a particular adsorbent at adsorption equilibrium. It depends upon the nature of both the
adsorbate as well as adsorbent.
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Surface Chemistry
Types of adsorption : The adsorption is classified into two types :
(i) Physical adsorption (i.e. physisorption) : When the particles of the adsorbate are held to the surface of
the adsorbent by the physical forces such as van der Waalís forces, the adsorption is called physical
adsorption or vanderwaals adsorption.
(ii) Chemical adsorption (i.e. chemisorption) :
When the molecules of the adsorbate are held to the surface of the adsorbent by the chemical forces, the
adsorption is called chemical adsorption.
Difference between physical adsorption and chemical adsorption

Physical Adsorption Chemical Adsorption
 The forces between the adsorbate molecules The forces between the adsorbate molecules
and the adsorbent are weak van der Waalís and the adsorbent are strong chemical forces.
forces.
 Low heat of adsorption of the order of High heat of adsorption of the order
20-40 kJ molñ1 80-240 kJ molñ1
 Usually occurs at low temperature and It occurs at high temperature
decreases with increasing temperature.
 It is reversible. It is irreversible.
 The extent of adsorption depends upon There is no correlation between extent of
the ease of liquefication of the gas. adsorption and the ease of liquefication of gas.
 It is less specific in nature, all gases are It is highly specific in nature and occurs only
adsorbed on the surface of a solid to some when there is bond formation between
extent. adsorbent and adsorbate molecules.
 It forms multimolecular layers. It forms mono-molecular layer.
 extent of adsorption (x/m) increases with extent of adsorption (x/m) increases with pressure
pressure
 Competitive adsorption : When an adsorbent is in contact with more than one species (adsorbate). There
will be competition among them to get adsorbed on to the surface of the adsorbent. The one that is more
strongly adsorbed gets deposited first in preference to the others. Further a strongly adsorbed substance
may displace a weakly adsorbed substance.
Ex. NH3 can displace O2 or N2 from the surface of charcoal.
Adsorption of gases on solids :
The extent of adsorption of a gas on a solid surface is affected by the following factors:
 The nature of the gas (i.e. nature of the adsorbate). The easily liquefiable gases such as HCl, NH3, Cl2
etc. are adsorbed more than the permanent gases such as H2, N2 and O2. The ease with which a gas can be
liquefied is primarily determined by its critical temperature. Higher the critical temperature (Tc) of a gas, the
more easily it will be liquefied and, therefore, more readily it will be adsorbed on the solid.
Gas SO2 CH4 H2
TC 330K 190 K 33 K
 Nature of adsorbent. The extent of adsorption of a gas depends upon the nature of adsorbent. Activated
charcoal (i.e. activated carbon), metal oxides (silica gel and aluminium oxide) and clay can adsorb gases
which are easily liquified. Gases such as H2, N2 and O2 are generally adsorbed on finely divided transition
metals Ni and Co.
 Activation of adsorbent :
(a) Metallic adsorbents are activated by mechanical rubbing or by subjecting it to some chemical reactions.
(b) To increase the adsorbing power of adsorbents, they are sub-divided into smaller pieces. As a results, the
surface area is increased and therefore, the adsorbing power increases.
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Surface Chemistry
 Effect of temperature :Mostly the process of adsorption is exothermic and the reverse process or desorption
is endothermic. If the above equilibrium is subjected to increase in temperature, then according to Le-
Chaterlierís principle, with increase in temperature, the desorption will be favoured. Physical adsorption
decreases continuously with increase in temperature whereas chemisorption increases initially, shows a
maximum in the curve and then it decreases continuously.
x x
m m
Temperature Temperature
The initial increase in chemisorption with increase in temperature is because of activation energy required.
This is why the chemical adsorption is also known as ìActivated adsorptionî.
A graph between degree of adsorption (x/m) and temperature ëtí at a constant pressure of adsorbate gas is
known as adsorption isobar.
 Effect of pressure. The extent of adsorption of a gas per unit mass of adsorbent
depends upon the pressure of the gas. The variation of extent of adsorption
expressed as x/m (where x is the mole of adsorbate and m is the mass of the
adsorbent) and the pressure is given as below. A graph between the amount of
adsorption and gas pressure keeping the temperature constant is called an
adsorption isotherm.
It is clear from the figure-1 that extent of adsorption (x/m) increases with pressure and becomes maximum
corresponding to pressure Ps called equilibrium pressure. Since adsorption is a reversible process, the
desorption also takes place simultaneously. At this pressure (Ps) the amount of gas adsorbed becomes
equal to the amount of gas desorbed.
Freundlich Adsorption isotherm :
The variation of extent of adsorption (x/m) with pressure (P) was given mathematically by Freundlich.
 At low pressure the graph is almost straight line which indicates that x/m is directly proportional to the
pressure. This may be expressed as :
(x/m)  p or (x/m) = kp where k is constant.
   At high pressure the graph becomes almost constant which means that x/m becomes independent of
pressure. This may be expressed as :
(x/m) = constant or (x/m)  p0 (since p0 = 1) or (x/m) = kp0.
   Thus, in the intermediate range of pressure, x/m will depend upon the power of pressure which lies between
0 to 1, fractional power of pressure. This may be expressed as
(x/m)  p1/n or (x/m) = kp1/n
Where n can take any whole number value which depends upon
the nature of adsorbate and adsorbent. The above relationship is
also called Freundlichís adsorption isotherm. Slope=(1/n)
The constant k and n can be determined as explained below : log(x/m)
Taking logarithms on both sides of
Eq. (x/m) = kp1/n we get intercept = log k
log p
log (x/m) = logk + (1/n) log p.
 One of the drawbacks of Freundlich isotherm is that it fails at high pressure of the gas.
 This equation applicable only when adsorbate substance form unimolecular layer on adsorbent
surface. i.e. chemical adsorption.
Adsorption from solutions : The process of adsorption can take place from solutions also. It is observed that
solid adsorbents adsorb certain solutes from solution in preference to other solutes and solvents. For
example, animal charcoal decolouries impure sugar solution by adsorbing colouring dye in preference to
sugar molecules.
The extent of adsorption from solution depends upon the concentration of solute in the solution as given by
Freundlich isotherm : (x/m) = k(c)1/n (n  1)
where c is the equilibrium concentration of the solute in solution.
Temperature dependence here also is similar to that for adsorption of gases and in place of equilibrium
pressure, we use equilibrium concentrations of the adsorbates in the solution.
AIPMTSCH -3
Surface Chemistry
Applications of adsorption :
 In gas masks : Activated charcoal is generally used in gas masks to adsorb poisonous and toxic gases
from air. These masks are commonly used by the miners because there are poisonous gases like CO, CH4
etc. in the atmosphere in coal mines.
   In dyeing of cloths : Mordants such as alums are used in dyeing of cloths. They adsorb the dye particles
which, otherwise, do not stick to the cloths.
   In dehumidizers : Silica gel is commonly used to adsorb humidity or moisture from air.
 Removal of colouring matter : Many substances such as sugar, juice and vegetable oils are coloured due
to the presence of impurities. They can be decolourised by placing them in contact with adsorbents like
activated charcoal or fullerís earth.
 Heterogeneous catalysis : The phenomenon of adsorption is useful in the heterogeneous catalysis. The
metals such as Fe, Ni, Pt, Pd, etc, are used in the manufacturing processes such as Contact process,
Haber process and the hydrogenation of oils. Their use is based upon the phenomenon of adsorption.
 Refining Petroleum : Silica gel is used as adsorbent in petroleum refining.
 Chromatography : It is a method for separation of component and is based on preferential adsorption
column is very common device used.
 Creating vacuum : High vacuum can be created by removing gas by adsorption.
 Adsorption Indicators : In volumetric analysis, adsorption indicator is used Surface of certain precipitates
such as silver halide have the property of adsorbing some dye like eosin, fluorescein, etc In the case of
precipitation titration (AgNO3 vs NaCI) of the indicator is adsorbed at the end point producing a characteristic
colour on the precipitate.
 In froth floatation process : (in metallurgy).
 Softening of hard water : Ion exchange resins used for softening of hard water is based upon selective and
competive adsorption of ions on resins.
Na2Z + Ca+2  CaZ + 2 Na+
The organic polymers containing groups like ñCOOH, ñSO3H and ñNH2 etc. possess the property of selective
adsorption of ions from solution. These are quite useful in the softening of water.
Example-1 A sample of charcoal weighing 6 g was brought into contact with a gas contained in a vessel of one
litre capacity at 27@C. The pressure of the gas was found to fall from 700 to 400 mm. Calculate the
volume of the gas (reduced to STP) that is adsorbed per gram of the adsorbent under the condition
of the experiment (density of charcoal sample is 1.5 g cm3).
Solution. The adsorption is taking place in a closed vessel hence if pressure falls there is correspondingly
increase in volume constant, excess of the volume of the gas would be adsorbed.
P1V1 = P2V2
V1 1000
V2 = P1 = 700 E = 1750 mL.
P2 40
6.00
Actual volume of the flask = 1000 ñ volume of charcoal = 1000 ñ = 996 mL.
1.50
Volume of the gas adsorbed = 1750 ñ 996 = 754 mL.

P1V1 P2 V2 
Volume of the gas adsorbed per gram at STP  U sin g T  T 
 1 2 
125 .67  400  273
= = 60.19 mL.
300  760
 Catalysts : Berzillus in 1835 used the word catalyst first time for some substance which alter rate of chemical
reaction and themselves remain chemically and quantitatively unchanged after the reaction and the phenomenon
is known as catalysis.
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Surface Chemistry
Eg : Potassium chlorate when heated at 653K to 873K, it gives O2, When MnO2 is used in this reaction the
O2 is quickly at the low temperature hence MnO2 is a catalyst
2KCIO3 2KCI + 3O2
 Homogeneous Catalysis : When catalysts and reactants are in same phase then the process is said to be
homogeneous catalysis and
Eg : (i) 2SO 2 (g)  O 2 (g)   2SO3 (g)
NO( g )
(ii) CH3 COOCH3 ()   CH3 COOH(aq)

HCl(  )
H2SO 4 (  )
(iii) C12H22O11(aq.)  H2O()   C 6H12 O 6 (aq.)  C 6H12O 6 (aq.)
Glucose Fructose
 Heterogenous Catalysis : When catalysts and reactants are in different phases, then process a know as
heterogenous catalysis and catalyst is called heterogeneous catalyst
Eg : (i) 2SO 3 (g)  O 2 (g)   2SO3 (g)
Pt ( s )
(ii) N2 (g)  3H2 (g)   2NH3 (g)

Fe( s )
(iii) 4NH3 (g)  5O 2 (g)   4NO(g)  6H2O(g)

Pt ( s )
(iv) Vegetable oils ()  H2 (g)   Vegetable ghee (s).

Ni( s )
 Types of Catalysis
(a) Positive Catalysis : A substance which increase the rate of chemical reaction is called positive
catalyst and this process called positive catalysis.
Pt( s ) Fe(s)
(i) 2SO 2 (g)  O 2 (g)     2SO 3 (g) (ii) N2 (g)  3H2 (g)   2NH3 (g)
positive catalyst positive catalyst
(b) Negative Catalysis : A substance which decrease the rate of chemical reaction is called negative
catalyst and this process called negative catalysis.
H PO or glycerol
Eg : (i) 2H2O2 3 
4   2H2O  O2
negative catalyst
(ii) Decomposition of chloroform reduces in the presence of 1% ethyl alcohol.
1 1% ethyl alcohol
CHCl3  O 2      COCl2  HCl
2 negative catalyst
(iii) T.E.L. is used as negative catalyst in petrol which reduce knocking.
(c) Auto Catalysis : When one of the reaction product behave as catalyst for that reaction and increase
the rate of reaction then the phenomenon is called autocatalysis.
ìAuto catalytic reactions are slow in the beginning but become increasingly rapid as the reaction
proceeds.
Eg : (i) CH3COOC 2H5  HOH  CH3 COOH( Auto catalyst )  C 2H5OH
(ii) 2KMnO 4  5 C OOH  3H2 SO 4  K 2 SO 4  MnSO 4 ( Auto catalyst)  8H2 O  10CO 2

|
COOH
(d) Induced Catalyst : When one reaction catalyse an other reaction than the phenomenon is called
induced catalysis and that reaction is called induced catalyst.
Promoters/Activators : Substance which themselves are not catalyst but its presence can increase the
catalytic activity of catalyst. A promoters increase the number of active sites on the surface Eg :
(i) N 2  3H2    2NH 3

Fe ( catalyst )
Mo ( promoter )
Vegetable Oil + H2 Cu( promoter

  Vegetable ghee.
Ni( catalyst )
(ii) )
(iii) CO  2H 2    CH 3 OH
ZnO ( catalyst )
Cr2 O 3 ( promoter )
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Surface Chemistry
Catalytic Poisons/ Anti catalysts/ Catalyst Inhibitor : Substance which themselves are not catalyst
but whose presence decrease the activity of the catalyst. Poisoning is due to preferential adsorption of
poison on the surface of the catalyst.
Fe ( catalyst )
(i) N 2  3H 2         2NH 3
CO / H 2 S ( catalytic poisons )
Platinised asbestos ( catalyst )

(ii) 2SO 2  O 2                 2 SO 3
As 2 S 3 ( catalytic poisons )
(iii) Rosunmund Reactions : RCOCl  H2  

Pd ( catalyst )
 RCHO  HCI
BaSO 4 ( poisons catalytst )
  Characteristics of Catalysis :
(i) A Catalyst remains unchanged in mass and chemical compositions at the end of reactions. However
its physical state can be change. Eg :
Granular MnO2 during decomposition of KClO3 is left as powder at the end of the reaction.
(ii) Finely devided state of catalyst is more efficient for the reactions because surface area increases
and more adsorption take place.
(iii) A small amount of catalyst is generally sufficient to catalyse almost unlimited reaction but in some
cases the rate of reaction depends on amount of catalyst.
Exception : (a) In Friedal Craft reaction more amount of catalyst is required.
(b) Hydrolysis of ester in acidic and alkaline medium its rate of reaction is proportional to
concentration of H+ or OHñ ions.
(iv) A catalyst cannot initiate reaction. But some times the activation energy is so large that practically
a reaction may not start until a catalyst lowers the activation energy significantly. For example,
mixture of hydrogen and oxygen do not react at room temperature but the reaction occurs very rapid
in presence of Pt black.
room temperature
H2 + O2    No reaction
Pt black
H2 + O2   H2O.
(v) Catalyst are generally specific in nature. A substance which act as a catalyst in a particular reaction,
fails to catalyse other reaction.
(vi) Catalyst cannot change equilibrium state but it help to attain equilibrium quickly.
(vii) A catalyst does not change the enthalpy, entropy and free energy of a reaction.
(viii) Optimum temperature : There is a particular temperature at which the efficiency of a catalyst a
maximum this temperature is known as optimum temperature. On either side the optimum
temperature, the activity of catalyst decreases.
 Adsorption Theory of Heterogeneous Catalyst : This theory explain the mechanism of heterogeneous
catalyst. This theory is combination of two theory, intermediate compound formation theory and the old adsorption
theory, the catalytic activity is localised on the surface on the catalyst. The mechanism involve 5 steps.
(i) Diffusion of reactant to the surface of the catalyst.
(ii) Adsorption of reactant molecules on the surface of the catalyst.
(iii) Formation of activated intermediate.
(iv) Formation of reactions product on the catalyst surface.
(v) Diffusion of reactions product from the catalyst surface or desorption.
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Surface Chemistry
Examples :
Let us consider addition of H2 gas to ethelene in presence of Ni catalyst, the reaction take places as follows.
 Factors Supporting Theory :
(i) This theory explain the role of active centre, more free valency which provide the more space for the
more adsorption and concentration increases as a result increase in rate of reaction.
(ii) Rough surface has more active and pores there will be more free valency so more will be rate of
reaction.
(iii) The theory explain centre action of promoters which occupied more strain
interstial void as a result surface area for the adsorption increases H H
therefore rate of reaction increases.
Ni Ni surface area increase
promoters
inhibitors
(iv) The theory explain of function of poisons or inhibitors. In poisoning preferential
adsorption of poisons take place on the catalyst, surface area for the
adsorption on the catalyst decrease hence rate of reaction decreases.
catalyst
AIPMTSCH -7
Surface Chemistry
Some Industrial Catalytic reactions
Colloid Solution :
Colloid State : A substance is said to be in colloidal state when the size of the particle of disperse phase
is greater than particle of true solution and less than that of suspension solution particle, their range of
diameters between 1 and 1000 nm (10ñ9 to 10ñ6 m).
Colloid solution : It is a heterogeneous system consisting of 2 phase :
(1) Disperse Phase (D.P) : The phase which is dispersed through the medium is called dispersed phase or
discontinuous phase or internal phase.
(2) Dispersion Medium (D.M) : A medium in which colloidal particles are dispersed is called dispersion
medium. It is also known as continuous phase or outer phase or external phase.
Colloidal solution = D.P. + D.M.
Ex. In Gold sol, Gold is D.P and water is D.M.
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Surface Chemistry
Diffrenciating point of colloids :
(1) A colloid is a heterogeneous system in which one substance is dispersed (dispersed phase) as very fine
particles in another substance called dispersion medium.
(2) The solution and colloid essentially differ from one another by particle size.
* In a solution, the particles are ions or small molecules.
* In a colloid, the dispersed phase may consist of particles of a single macromolecule (such as
protein or synthetic polymer) or an aggregate of many atoms, ions or molecules.
(3) Colloidal particles are larger than simple molecules but small enough to remain suspended. They have a
range of diameters between 1 and 1000 nm (10ñ9 to 10ñ6 m).
Classification of colloids :
 1. On the basis of physical state of D.P. and D.M.
On the bases of physical state of D.P. and D.M. colloidal solution may be divided into eight system.
DP DM Type of colloid Examples
Solid Solid Solid Sol Some coloured glasses,

and gem stones
Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Liquid Aerosol Fog, mist, cloud,
insecticide sprays
Gas Solid Solid Sol Pumice stone, foam rubber
Gas Liquid Foam Froath, whipped cream, soap lather.
* Solution of gas in gas is not a colloidal system because it form homogeneous mixture.
2. On the Basis of interaction of D.P. for D.M. : There are two types-
(i) Lyophilic colloids / liquid loving sols / intrinsic colloid. The colloidal solution in which the particles of
the dispersed phase have a great affinity (or love) for the dispersion medium, are called lyophilic colloids.
These solutions are easily formed and the lyophilic colloids are reversible in nature. In case water acts as the
dispersion medium, the lyophilic colloid is called hydrophilic colloid. The common examples of lyophilic
colloids are glue, gelatin, starch, proteins, egg albumin, rubber, etc.
(ii) Lyophobic colloids / solvent hating colloid / extrinsic colloid. The colloidal solutions in which there
is no affinity between particles of the dispersed phase and the dispersion medium are called lyophobic
colloids. Such solutions are formed with difficulty only by special methods. These sols are readily precipitated
(or coagulated) on the addition of small amounts of electrolytes, by heating or by shaking and hence are not
stable. Further, once precipitated, they do not give back the colloidal sol by simple addition of the dispersion
medium. Hence these sols are also called irreversible sols. They need stabilising agents for their preservation.
In case the dispersion medium is water, the lyophobic sol is called hydrophobic colloid. For example, the
solution of metals like Ag and Au, hydroxides like Al (OH)3, Fe(OH)3, metal sulphides like As2S3 etc.
* Lyophilic sols are more stable than lyophobic sols, the additional stability is due presence of an envelope
of the solvent layer (say water) around the colloidal particle, the process is known as hydration, To coagulate
a hydrophilic sols we have to add a dehydrating agent in addition to electrolyte.
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Surface Chemistry
DISTINCTION BETWEEN LYOPHILIC AND LYOPHOBIC COLLOIDS
S.No. Property Lyophilic colloids Lyophobic colloids
1 Ease of preparation There are easily formed by direct mixing. These are formed only by special methods
Reversible or
2 These are reversible in nature These are irreversible in nature.
irreversible nature
The particles of colloids are true The particles are aggregates of many
3 Particles nature
molecules but are big in size molecules
These are unstable and require traces of
4 Stability These are very stable
stabilizers
The addition of small amount of
5 Action of electrolytes No effect electrolytes causes precipitation (called
coagulation) of colloidal solution.
The particles move in a specific direction
either towards anode or cathode
6 Charge on particles The particles do not carry any charge.
depending upon their charge in an electric
field
The particles of colloids are heavily
The particles of colloids are not
7 Hydration hydrated due to the attraction for the
appreciably hydrated.
solvent.
The viscosity and surface tension of the The viscosity and surface tension are
8 Viscosity sols are less than that of the dispersion nearly the same as that of the dispersion
medium medium.
9 Tyndall effect They do no show tyndall effect They show tyndall effect.
3. On the basis of charge of on particles

(i) positive Sol
(a) Metal Oxide & Hydroxide - SnO2, TiO2, Fe2O3, AI(OH)3, Fe(OH)3, Cr(OH)3.
(b) Basic Dyes Methylene blue, vismark brown.
(ii) negative Sol -
(a) Metal sol - Ag, Au, Pt, Cu
(b) Acidic dye - congo red, eosin
(c) Sulphide Sol- CdS, HgS, As2S3, Sb2S3.
(d) Natural sol - Blood, clay, charcoal, latex rubber, dust particle in water, starch carbon particle in smoke, gum.
4. Other type of colloids : Multimolecular, macromolecular and associated colloids
 Multimolecular colloids : In this type, the particles consist of an aggregate of atoms or small molecules
size less than 1 nm. For example, sols of gold atoms and sulphur (S8) molecules. In these colloids, the
particles are held together by van der Waalís forces.
 Macromolecular colloids : In this types, the particles of the dispersed phase are sufficiently big in size
(macro) to be of colloidal dimensions. These macromolecules forming the dispersed phase are generally
polymers having very high molecular masses. These colloids are quite stable and resemble true solutions in
many respects. Naturally occuring macromolecules are starch, cellulose, proteins, enzymes, gelatin, etc.
 Associated colloids (Micelles): These are the substances which behave as normal strong electrolytes at
low concentration but behave as colloidal particles at higher concentration. These associated particles are
also called micelles. Ex. Soap.
Micelles : There are some substances which at low concentrations behave as normal strong electrolytes
but at higher concentrations exhibit colloidal behaviour due to the formation of aggregated particles. The
aggregated particles thus formed are called micelles. These are also known as associated colloids. The
formation of micelles takes place only above a particular temperature called Kraft Temperature (Tk) and
above a particular concentration called Critical Micelle Concentration (CMC). On dilution, these colloids
revert back to individual ions. Surface active agents such as soaps and synthetic detergents belong to this
class. For soaps, the CMC is ~ 10ñ4 to 10ñ3 mol Lñ1. These colloids have both lyophobic and lyophilic parts.
Micelles may contain as many as 100 molecules or more.
AIPMTSCH - 10
Surface Chemistry
Mechanism of micelle formation: Let us take the example of soap solutions. Soap is sodium salt of a
higher fatty acid and may be represented as RCOOñNa+ e.g., sodium stearate viz.CH3(CH2)16COOñ Na+
which is a major component of many bar soaps. When dissolved in water, it dissociates into RCOO- and Na+
ions. The RCOOñ ions, however, consist of two parts i.e., long hydrocarbon chain R (also called non-polar
'tail') which is hydrophobic (water repelling) and the polar group COOñ (also called polar-ionic 'head') which is
hydrophilic (water loving). The RCOOñ lons are, therefore, present on the surface with their COOñ groups in
water and the hydrocarbon chains R staying away from it, and remain at the surface, but at higher concentration
these are pulled into the bulk of the solution and aggregate in a spherical form with their hydrocarbon chains
pointing towards the centre with COOñ part remaining outward on the surface. An aggregate thus formed is
known as ëIonic micelle'. These micelles may contain as many as upto 100 such ions.
Aggregation of RCOOñ ions to form an ionic micelle.

Similarly, in case of detergents, e.g., sodium lauryl sulphate viz.
CH3(CH2)11SO4ñ Na+, the polar group is ñ SO4ñ along with the long
hydrocarbon chain. Hence, the mechanism of micelle formation is
same as that of soaps.
Critical micelle concentration [CMC] : The minimum concentration required for micelle formation is
called critical micelle concentration. Its value depends upon the nature of D.P. and D.M. For eg. Surface
active agent (surfactants, which decrease the surface tension) like soaps and detergents form micelle beyond
CMC (~10ñ3 mol/litre for soaps).
* Usually longer the hydrophobic chain, smaller is its CMC.
* Also CMC increase with decreasing polarity of the D.M.
* The micelles ëformation takes place only above a particular temperature called as Kraft Temperature (Tk ).
*At CMC, the micelles are spherical in shape, but that start flattening with increase in concentration and
ultimately form sheet or film like structures which have a thickness of two molecules. These are called
lamelar micelles or McBain Micelles.
Example of micelles :
(i) Sodium stearate C17H35COOñNa+(Soap).
(ii) Sodium lauryl sulphate CH3 [CH2]11 SO4ñ Na+ (Detergent).
(iii) Cetyl trimethyl ammonium bromide (Detergent). CH3(CH2)15N+(CH3)3Brñ.
ñ +
(iv) Sodium p-dodecylbenzenesulphonate (Detergent) : C12H25 SO3 Na
(v) Acidic (negative colloids) and basic (positive colloids) dyes.

The Cleansing Action of Soaps : It has been mentioned earlier that a micelle consists of a hydrophobic
hydrocarbon like central core. The cleansing action of soap is due to these micelles, because oil and grease
can be solubilised in their hydrocarbon, like centres which are not otherwise soluble in water. This is shown
diagrammatically in Figure The dirt goes out along with the soap micelles.
Sodium stearate (C17H35COOñ Na+) Hydrophobic tail

(a) (b)
(c) (d) (e)

Fig. : The cleansing action of soap.
AIPMTSCH - 11
Surface Chemistry
(a) A sodium stearate molecule
(b) The simplified representation of the molecule that shows a hydrophilic head and a hydrophobic tail
(c) Grease (oily substance) is not soluble in water
(d) When soap is added to water, the non-polar tails of soap molecules dissolve in grease
(e) Finally, the grease is removed in the form of micelles containing grease.
*Surfactants : They can be ionic as well as non-ionic. The ionic are soaps and detergent. The surfactant
gets adsorbed at the interface between the dispersed droplets and dispersion medium in a form of mono
molecular layer and lowers the interfacial tension between oil and water so as to facilitate the mixing of two
liquids.
Preparation of lyophobic colloidal sols :

[A] Condensation methods :
In these methods particles of atomic or molecular size are induced to combine to form aggregates having
colloidal dimensions. For this purpose chemical as well as physical methods can be applied.
(a) Chemical methods. Colloidal solutions can be prepared by chemical reactions leading to formation of
molecules by double decomposition, oxidation, reduction or hydrolysis. These molecules then aggregate
leading to formation of sols.
(i) Double decomposition : When a hot aqueous dilute solution of arsenous oxide (As2O3) is mixed with a
saturated solution of H2S in water, a colloidal sol of arsenous sulphide (As2S3) is obtained.
Double decomposit ion
As2O3(in hot water) + 3H2S (saturated solution in H2O)          As2S3(sol) + 3H2O
(ii) Oxidation : A colloidal sol of sulphur is obtained by passing H2S into a solution of sulphur dioxide.
Oxidation
SO2 + 2H2S(saturated solution in H2O)    3S(sol) + 2H2O
Sulphur sol can also be obtained when H2S is bubbled through Br2 water or nitric acid (oxidizing agent).
(iii) Reduction : Colloidal sol of metals like gold, silver solution are obtained by following method.
2 AuCl3 + 3 HCHO + 3H2O  2Au(sol) + 3HCOOH + 6HCl.
(purple of cassius)
(iv) Hydrolysis : A colloidal sol of metal hydroxides like Al(OH)3 or Cr(OH)3 is obtained by boiling a dilute
solution of FeCl3 , AlCl3 or CrCl3 .
FeCl3 + 3H2O  Fe(OH)3 (sol) + 3HCl ; AlCl3 + 3H2O  Al(OH)3 (sol) + 3HCl
The colloidal sol of sillicic acid is also obtained by hydrolysis of dilute solution of sodium silicate with
hydrochloric acid. Na4SiO4 + 4HCl  Si(OH)4 (sol) + 4NaCl.
(b) Physical methods : The following physical methods are used to prepare the colloidal solutions.
(i) By Exchange of solvent : When a true solution is mixed with an excess of the other solvent in which the
solute is insoluble but solvent is miscible, a colloidal sol is obtained. For example,
 when a solution of sulphur in alcohol is poured in excess of water, a colloidal sol of sulphur is obtained.
 when a solution of phenolphthalein in alcohol is poured in excess of water a white sol of phenolphthalein is
found.
Phenolphthalein, I , sulphur sol can be prepared by this methods.
2
(ii) Excessive cooling : Molecules of certain substance condense together on excess cooling to form
colloidal size particle. The colloidal sol of ice in an organic solvent such as CHCl3 or ether can be obtained by
freezing a solution of water in the solvent. The molecules of water which can no longer be held in solution
separately combine to form particles of colloidal size.
AIPMTSCH - 12
Surface Chemistry
[B] Dispersion Methods : In these methods large particles of the substance are broken into particles of
colloidal dimensions in the presence of dispersion medium. These are stabilized by adding some suitable
stabilizer. Some of the methods employed are given below :
(a) Electrical disintegration or Bredig's Arc method : This

process involves dispersion as well as condensation. Colloidal sols
of less reactive metals such as gold, silver, platinum, copper, lead
etc., can be prepared by this method. In this method, electric arc
is struck between electrodes of the metal immersed in the
dispersion medium as shown in fig. The intense heat produced
vaporises the metal, which then condenses to form particles of
colloidal size by surrounding cooling mixture (ice).
*A slight trace of KOH is added in water to stabilized colloidal solutions.
(b) Peptization: The term has originated from the digestion of proteins by the enzyme pepsin. Peptization
may be defined as (the process of converting a precipitate into colloidal sol by shaking it with dispersion
medium in the presence of a small amount of electrolyte).
The electrolyte used for this purpose is called peptizing agent. This method is applied, generally, to convert
a freshly prepared precipitate into a colloidal sol. During peptization, the precipitate adsorbs one of the ions
of the electrolyte on its surface.
The ion adsorbed on the surface is common either with
the anion or cation of the electrolyte. This causes the
development of positive or negative charge on precipitates
which ultimately break
up into smaller particles having the dimensions of colloids.
For example :
(i) When freshly precipitated Fe(OH)3 is shaken with aqueous solution of FeCl3 (peptizing agent) it adsorbs
Fe3+ ions and thereby breaks up into small-sized particles.
FeCl3  Fe3+ + 3Clñ ; Fe(OH)3 + Fe3+  Fe(OH)3 | Fe3+
+3 +3
+3
+3 +3 +3 +3
+3 +3
+3 +3 +3
3+
+3
+ Fe +3 +3
+3 +3 +3
Peptizing agent +3
+3 +3 +3 +3 +3 +3
ppt of Fe (OH)3 +3
+3 +3
+3 +3
+3 +3 +3 +3
+3 +3
Charge Colloidal particals of Fe (OH)3

(ii) Freshly prepared stannic oxide on treatment with a small amount of dilute hydrochloric acid forms a
stable colloidal sol of stannic oxide, SnO2 ; Sn4+ .
SnO2 + 4HCl  Sn4+ + 2H2O + 4Clñ ; SnO2 + Sn4+  SnO2 / Sn4+ .
(iii) Freshly precipitated silver chloride can be converted into a colloidal sol by adding a small amount of
hydrochloric acid, AgCl : Clñ .
(iv) Cadmium sulphide can be peptised with the help of hydrogen sulphide, CdS : S2ñ .
Purification of Colloidal Sols : The colloidal sols obtained by various methods are impure and contain
impurities of electrolytes and other soluble substances. These impurities may destabilise the sol. Hence,
they have to be removed. A very important method of removal of soluble impurities from sols by a semipermeable
membrane is known as dialysis.
A. Dialysis : It is a process of removing a dissolved substance from a colloidal solution by means diffusion
through suitable membrane. Since particles in true solution (ions or smaller molecules) can pass through
animal membrane or parchment paper or cellophane sheet but colloidal particle do not, the appratus used for
this purpose is called Dialyser.
AIPMTSCH - 13
Surface Chemistry
A bag of suitable membrane containing the colloidal solutions
is suspended in a vessel through which fresh water
continously flow. The molecules and ions (crystalloids) diffuse
through membrane into the outer water & pure colloidal
solution is left behind.
Movement of ions across the membrane can be expedited
by applying electric potential through two electrodes as shown
in fig.
This method is faster than simple dialysis and is known as
Electrodialysis.
*The most important applications of dialysis is in the purification of blood in the artificial kidney machine. In
case of kidney failure, blood cannot be purified. under such condition, the blood is separated from dissolved
toxic impurities by dialysis and re-introduced in the bloods stream.
*Dialysis is not applicable for non-electrolytes like glucose, sugar, etc.
B. Ultra Filtration : In this method, colloidal sols are purified by carrying out filtration through special type
of graded filters called ultra-filters. These filter papers allow only the electrolytes to pass through. These filter
papers are made of particular pore size by impregnating with colloidal solution and subsequently hardened
by soaking in formaldehyde collodion. In order to accelerate the filtration through such filter papers, increased
pressure or section is employed.
Example-2 When SO2 is bubbled into H2S gas, colloidal sol is formed. What type of colloidal sol is it ?
Solution. 2H2S + SO2  2H2O + 3S (colloidal).
Lyophobic colloidal sol of sulphur is formed.
Example-3 A reddish brown positively charged sol is obtained by adding small quantity of FeCl3 solution to
freshly prepared and well washed Fe(OH)3 precipitate. How does it take place ?
Solution. It is due to adsorptions of Fe3+ ions on the surface of Fe(OH)3 which gives colloidal sol.
Fe(OH)3 (ppt.) + Fe3+ (ions adsorbed)  [Fe(OH)3]Fe3+ (colloidal sol).
Example-4 Suppose we have a cube of 1.00 cm length. It is cut in all three directions, so as to produce eight
cubes, each 0.50 cm on edge length. Then suppose these 0.50 cm cubes are each subdivided into
eight cubes 0.25 cm on edge length, and so on. How many of these successive subdivisions are
required before the cubes are reduced in size to colloidal dimensions of 100 nm.
Solution. We find that every division in two equal halves also reduces the size of edge lengths to one half.
1
In first subdivision 1 cm is reduceds to 0.5 cm = cm.
2
2
1  1
In second subdivision 0.5 cm is reduced to 0.25 cm = cm =   cm
4 2
n
 1
In n subdivision 1 cm is reduced to   . Size of colloidal particles lies between 1 to 1000 mm.
2
Thus to make n subdivision required particle size may be attained.
n
 1
  = 100 nm = 100 E 10ñ9 m = 100 E 10ñ7 cm.
2
 n log 2 = 5
n E 0.3010 = 5.
5
n= = 16.61 = 17 subdivisions are required for dimension of 100 nm.
0.3010
AIPMTSCH - 14
Surface Chemistry
Important properties of colloidal sols :
 Heterogeneous character :
Colloidal sols are heterogeneous in character as they consist of two phases.
(a) dispersed phase and (b) dispersion medium.
 Visibility : Due to scattering caused by the colloidal particles, it will appear as a bright spot
moving randomly.
 Filterability : Colloidal particles pass through an ordinary filter paper. However, the particle do not
pass through other fine membranes.
 Colligative Properties : Colloidal sols show the colligative properties viz. relative lowering of vapour
pressure, elevation in boiling point, depression in freezing point and osmotic pressure. However, due to high
average molecular masses of colloidal particles, mole fraction of the dispersed phase is very low. Hence, the
values of the colligative properties observed experimentally are very small. Only osmotic pressure
measurements are used in determining the molecular mass of polymers.
   Optical Properties-Tyndall effect : Tyndall, in 1869, observed that if a strong beam of light is
passed through a colloidal sol placed in a dark place, the path of the beam gets illuminated. This phenomenon
is called Tyndall effect, which is due to the scattering of light by the colloidal particles. The illuminated path
of beam is called Tyndall cone. This phenomenon is due to scattering of light from the surface of colloidal
particles. In a true solution there are no particles of sufficiently large diameter to scatter light & hence the
beam is invisible.
Eye
microscope
Tyndall cone
Light source
Scattered light
True solution Colloidal solution
*The intensity of scattered light depends on the difference between the refractive indice of the D.P and D.M.,
In lyophobic colloids, this difference is appreciable and therefore the tyndal effect is quite well defined but in
lyophilic sols the difference is very small and the tyndal effect is very weak. Thus in sols of silicic acid, blood
serum, albumin, etc. there is little or no tyndal effect.
Example of Tyndall Effect
 Blue colour of sky and sea water.
 Visibility of tail of comets.
 Light thrown from a projector in cinema hall.
 Appearance of dust particle in a semi darked room.
Application of Tyndall Effect :
(i) In making ultramicroscopes.
(ii) In finding heterogenity of solution.
Example-5 Under what conditions is Tyndal effect observed ?

Solution. Tydalls effect is applicable when :
(a) The diameter of the dispersed particles is not much smaller than the wavelength of the light used.
(b) The refractive indices of the dispersed phase and the dispersion medium must differ greatly in
magnitude.
AIPMTSCH - 15
Surface Chemistry
Example-6 In the lower layer of the atmosphere, there is a great deal of dust. When the weather is fine, it is
possible to see the magnificent red colour of the setting sun. What have these observation to do with
colloids ?
Solution. Dust in the atmosphere is often colloidal. When the sun is low down on the horizon, light from it has
to pass through a great deal of dust to reach your eyes. The blue part of the light is scattered away
from your eyes. You see the red part of the spectrum, which remains. Red sunsets are the Tyndall
effect on a large scale.
 Mechanical Properties :

Brownian movement: Robert Brown, a botanist, discovered in
1827 that pollen grains placed in water do not remain at rest but
move about continuously and randomly. Later on, this phenomenon
was observed in case of colloidal particles when they were seen
under an ultramicroscope. The particles were seen to be in constant
zig-zag motion as shown in fig. This zig-zag motion is
called Brownian movement.
Brownian movement arises because of the impact of the molecules of the dispersion medium with the
colloidal particles. It has been postulated that the impact of the molecules of the dispersion medium on the
colloidal particle are unequal leading to zig-zag motion. However, as the size of the particle increases, the
effect of the impacts average out and the Brownian movement becomes slow. Ultimately, when the dispersed
particle becomes big enough to acquire the dimensions of suspension, no Brownian movement is observed.
Factors Affecting Brownian Movement :
(i) If particles is large then brownian movement becomes less.
(ii) Brownian movement increases with increasing temperature.
(iii) The brownian movement does not change with time & remains same for months or even for a year.
 Important :
(i) In confirmation of kinetic energy.
(ii) Determination of Avogadro numbers.
(iii) Stability of colloidal solution : Brownian movement does not allow the colloidal particles to settle
down to gravity & thus is responsible for their stability.
 Electrical Properties (Electrophoresis) : The particles of the colloids are electrically charged and
carry positive or negative charge. The dispersion medium has an equal and opposite charge making the
system neutral as a whole. Due to similar nature of the charge carried by the particles, they repel each other
and do not combine to form bigger particles. That is why, a sol is stable and particles do not settle down.
Arsenious sulphide, gold, silver and platinum particles in their respective colloidal sols are negatively charged
while particles of ferric hydroxide, aluminium hydroxide are positively charged. The existence of the electric
charge is shown by the phenomenon of electrophoresis. It involves the 'movement of colloidal particles either
towards the cathode or anode, under the influence of the electric field'. The apparatus used for electrophoresis
as shown in fig.
(Fig. : A set up for electrophoresis.)

The colloidal solution is placed in a U-tube fitted with platinum electrodes. On passing an electric current, the
charged colloidal particles move towards the oppositely charged electrode. Thus, if arsenic sulphide sol is
taken in the U-tube, in which negatively charge particle of arsenic sulphide move towards the anode.
AIPMTSCH - 16
Surface Chemistry
*Earlier this process was called cataphoresis because most of the colloidal sols studied at that time were
positively charged and moved towards cathode.
Isoelectric point : The H+ concentration at which the colloidal particles have no charge is known as the
isoelectric point. At this point stability of colloidal particles becomes very less & do not move under influence
of electric field.
Fe(OH)3 sol prepared by the hydrolysis of FeCl3 solution adsorbs Fe3+ and this is positively charged.
ñ
FeCl3 + 3H2O Fe(OH3) + 3HCl ; Fe(OH)3 + FeCl3  Fe(OH)3 Fe3+ : 3Cl
Fixed part Diffused part.
Positive charge on colloidal sol is due to adsorption of Fe3+ ion (common ion between Fe(OH)3 and FeCl3).
As2S3 colloidal sol is obtained when As2O3 is saturated with H2S :
As2O3 + 3H2S  As2S3 + 3H2O.
As2S3 adsorbs S2ñ ions (common between H2S and As2S3 and thus is negatively charged).
As2S3 + H2S  As2S3 S2ñ : 2H+.
AgI in contact with AgNO3 forms positively charged colloidal sol due to adsorption of Ag+ ion.
AgI + AgNO3  [AgI]Ag+ : NO3ñ , AgI in contact with KI forms negatively charged colloidal sol due to
adsorption of Iñ ion AgI + KI  AgI Iñ : K+.
SnO2 in acidic medium forms positively charged colloidal sol due to adsorption of Sn4+ formed.
SnO2 + 4H+  Sn4+ + 2H2O SnO2 + Sn4+  SnO2 Sn4+
SnO2 in alkaline medium forms negatively charged colloidal sol due to adsorption of SnO32ñ formed.
SnO2 + 2OHñ  SnO32ñ + H2O SnO2 + SnO32ñ  SnO2 SnO32ñ
 Electric Double Layer Theory or Helm-holtz Electric double layer :

The surface of colloid particles acquire a positive or negative charge by the selective (preferential) adsorptions
of common ions carrying positive or negative charge respectively to form first layer. This layer attract counter
ions from D.M. form a second layer. The combination of two layers of opposite charge around the colloidal
particle is called Helm-holtz electric double layer. The first layer of ions is firmely held and is termed as fixed
layer while the second layer is mobile which is termed as diffused layer. The charge of opposite ions of fixed
and diffused layer double layer results in a difference in potential between two opposite charge layer is called
the electrokinetic potential or zetapotential which can be given by
Example :
When silver nitrate solution is added to KI solution, the precipitation of AgI adsorb iodide ions from
the D.M with the formation of fixed layer and negatively charged colloidal solution form, however when KI
solution is added to AgNO3 solution positive charge sol result due to the adsorbs of Ag+ ions from D.M.
AgI/Iñ AgI/Ag+
Negative charged Positively charged.
This fixed layer attracts counter ions from the medium forming a second layer.
Fixed layer
+
K
+
K
K+
Iñ
I
ñ Iñ K
+
ñ ñ
I AgI I
ñ
K+ I Iñ
Iñ Iñ Iñ K+
Zetapotential K+ +
K
K+ Diffused layer
AIPMTSCH - 17
Surface Chemistry
Example-7 Classify the following sols according to theirs charges :

(a) gold sol (b) ferric hydroxide sol (c) gelatine (d) blood
(e) sulphur (f) arsenious sulphide (g) titanium oxide.
Solution. Negatively charged colloidal sol : (a), (c), (d), (e), (f).
positively charged colloidal sol : (b), (g).
Example-8 SnO2 forms positively charged colloidal sol in acidic medium and negatively charged colloidal sol in
basic medium. Explain ?
Solution. SnO2 is amphoteric reacting with acid and base both. In acidic medium (say HCl) Sn4+ ion is formed
which is preferentially adsorbed on SnO2 giving positively charged colloidal sol :
SnO2 + 4HCl  SnCl4 + 2H2O ;
SnO2 + SnCl4  [SnO2]Sn4+(positively charged) + 4Clñ.
 Coagulation/Flocculation : The presence of small amounts of appropriate electrolytes is necessary

for the stability of the colloids. However, when an electrolyte is added in larger concentration; the particles of
the sol take up the ions which are oppositely charged and thus get neutralised. The neutral particles then
start aggregating giving particles of larger size which are then precipitated. This process of aggregation of
colloidal particles into an insoluble precipitate by the addition of some suitable electrolyte is
known as coagulation. At lower concentration of electrolytes, the aggregation of particles is called flocculation
that can be reversed on shaking while at higher concentration of electrolyte, coagulation takes place and the
same cannot be reversed simply by shaking. The stability of the lyophobic colloids is due to presence of
charge on colloidal particles. If, somehow, the charge is removed, the particles will come near to each other
to form aggregates and settled down under the force of gravity.
+ ++ + +
+ + + + ++ +
++
+ ++ +
+ ++ + + + + +
+ ++ + +
+ ++
+ ++ + +
+ ++ +
+ ++ +++ + ++
+ ++ + +
+ ++
+ ++
+ ++ +
+ + + + + ++ + + + +
+
+ + +
+ ++
+
+
+ +
+ + + + + + ++
+ + ++ + +
+ + ++ + ++ +
+ + + + +
+ + + + +
+ +
+ + +
+++ + + + + + +
+ + + + ++ + +
+ + + + ++ +
+ + + + ++ +
+ + ++
+
++
+ ++ ++
+ ++ +
+ ++ +
+ +++
+ + +
+
+ ++
+ ++
+++
+ ++
+ +
+
+
+
++
Neutralised
sol particles Coagulated sol
Coagulation of lyophobic sols can be carried out by the following methods.
(i) By electrophoresis
(ii) By mutual precipitation : It is a process in which oppositely charged sol are mixed in proper proportion
to neutralise the charge of each other causing coagulation of both the sol.
Example : Positively charged Fe(OH)3 and negatively charged As2S3 colloidal particle containing sol on
mixing get coagulated.
(iii) By Prolonged Dialysis : On prolonged dialysis, traces of the electrolyte present in the sol are removed
almost completely and the colloidal unstable and ultimately coagulate.
(iv) By Boiling : Sols such as sulphur and silver halides dispersed in water may be coagulated by boiling
because increased collisions between sol particle and the water molecule removed the adsorbed electrolytes.
This takes away the charge from the particles and helps them to coagulate.
(v) By cooling : Certain sol can also be coagulated by lowering temperature. For example, accumulation of
cream on the surface of milk on cooling. This is because at lower temperature the dispersion medium
molecules do not exert sufficient force on to the dispersed particles and hence the Brownian motion becomes
less effective.
(vi) By the addition of electrolyte : When excess of an electrolyte is added, the colloidal particles are
precipitated.
Coagulation value or Flocculation value : It needs to be noted that the coagulation of a colloidal solution
by an electrolyte does not take place until the added electrolyte has certain minimum concentration in the
solution. The minimum concentration of electrolyte in millimoles required to cause coagulation of
one litre of colloidal solution is called coagulation value. It is express in terms of millimoles/litre.
mil lim oles of electrolyte
Coagulation value = volume of sol in litre
AIPMTSCH - 18
Surface Chemistry
 Comparision of relative coagulating power of two electrolyte for the same colloidal solution :
The coagulation value decrease with increase in charge of the coagulating ion.
1
Coagulating power  coagulatio n value .
coagulatin g power of electrolyt e A coagulatio n value B

coagulatin g power of electrolyt e B = coagulatio n value A .
 Hardy-Schulze Rule : According to this rule greater is the valency of coagulating ion, greater its power to
cause precipitation. This is known as Hardy-Schulze.
In case of positive charged sol, the coagulating power of anion is in the order of [Fe(CN)6]4ñ > PO43ñ > SO42ñ > Clñ
In case of negative charged sol, the coagulating power of cation is in the order of Al3+ > Ba2+ > Na+.
 The coagulating power of bivalent ion is 20-80 times higher than monovalent ion and coagulating power of
trivalents is many times more than bivalent.
Example-9 The particles of a particular colloidal solution of arsenic trisulphide (As2S3) are negatively charged.
Which 0.0005 M solution would be most effective in coagulating this colloidal solution. KCl, MgCl2,
AlCl3 or Na3PO4? Explain.
Solution. Since As2S3 is a negatively charged colloidal sol hence positively charged ion will cause its coagulation.
By Hardy-Schulze rule ìgreater the charge on ion, greater the coagulating power to coagulate
oppositely charged colloidal solî, hence out of K+, Mg2+, Al3+ and Na+, Al3+ would be most effective.
Protective colloidal sols : Lyophilic colloidal sols are much more stable than lyophobic colloidal sols.
This is due to the extensive solvation of lyophilic colloidal sols, which forms a protective layer outside it and
thus prevents it from forming associated colloids. Lyophobic sols can easily precipitate by addition of small
amount of an electrolyte. They can be prevented from coagulation by previous addition of some lyophilic
colloid. This is due to formation of a protective layer by lyophilic sols outside lyophobic sols. Process of
protecting the lyophobic colloid solution from precipitation by an electrolyte due to previous addition of some
lyophilic colloid is called protection of colloid and lyophilic colloidal sols are called protective sols.
Eg : Gelatin, Sodium caseinate, Egg albumin, Gum arabic, Potato starch etc.,
Gelatin (lyophilic) protects gold sol (lyophobic) colloids is expressed in terms of gold number.
Gold Number : Zpsigmondy (1901) introduce a term called gold number it is defined as ëíthe minimum
amount of the protective colloid in milligrams which when added to 10 ml of a standard gold sol is just
sufficient to prevent a colour change from red to blue on the addition of 1 ml of 10% sodium chloride solution.
It may be noted that smaller of the gold number, greater will be protecting power of the protective colloid.
1
Protecting power  .
gold number
weight of lyophilic sol in mg 10
Gold Number = volume of gold sol in mL
The gold numbers of a few protective colloids are as follows :
Gelatin Haemoglobin Egg albumin Gum arabic Dextrin Starch
0.005 - 0.01 0.03 - 0.07 0.1 - 0.2 0.15 - 0.25 6 ñ 6.2 20 - 25
Uses of protective action :
(i) Gelatin is added in the preparation of ice cream to protect the particle of ice.
(ii) Protargol and Argyrol, is a silver sol protected by organic material used as eye drop.
Applications of Colloids : Colloids including emulsions find a number of uses in our daily life and
industry. Some of the uses are given below.
 In medicines : A wide variety of medicinal and pharmaceutical preparations are emulsions. Colloidial
medicines are easily adsorbed by the body tissue because of large surface area.
AIPMTSCH - 19
Surface Chemistry
* Colloidal antimony is used in curing kalaazar.
* Milk of magnesia, an emulsion, is used for stomach disorder.
* Colloidal gold is used for intramuscular injection.
* Colloidal sulphur are used as Germicides.
* Argyrol is a silver sol used as an eye lotion.
* Colloidal Fe(OH)3 is given to arsenic poisoning patients as it adsorbs arsenic and then gets omited out.
 Tanning : Animal hides are colloidal in nature. Which contain positive charge colloidal particles of protein.
This hide is kept in a tank containing tannic acid, which contains negatively charge colloidal particle. Therefore,
mutual coagulation takes place this results in hardening of leather, this process is termed as tanning of
leather. Chromium salts are also used in place of tannic acid.
 Photographic plate & Film : Photographic plate or films are prepared by coating an emulsion of the light
sensitive silver bromide in gelatin over glass plates or celluloid films. Gelatin prevent the coagulation of
colloidal particle of AgBr.
 Rubber plating : The negatively charged rubber particles from rubber sol are deposited on wares and
handles of different tools. Rubber gloves are formed by rubber plating on suitable templates.
 Sewage disposal : Sewage water contains charged colloidal particles of dirt, rubbish, etc., and these do
not settle down easily. The particles can be removed by discharging them at electrodes. Dirty water is
passed through a tunnel fitted with metallic electrodes which are maintained at high potential difference. The
particles migrate to the oppositely charged electrode, lose their charge and get coagulated. The deposited
matter is used as a manure and the water left behind is used for irrigation.
 Cottrell smoke precipitator :
Smoke is a dispersion of negatively charged
colloidal particles of carbon in air and can be
made free of these colloidal particles by passing
it through cottrell precipitator as shown in fig.
installed in the chimney of an industrial plant. It
consists of two metal discs charged to a high
potential. The carbon particles get discharged and
precipitate, while gases come out from the
chimney.
 Formation of deltas : The river water contains colloidal particles of sand and clay which carry negative
charge. The sea water contains +ve ions such as Na+, Mg2+, Ca2+, etc. As the river water meets sea water,
these ions discharge the sand or clay particle which are precipitated in the form of delta.
 Artificial rain : Cloud consists of charge particle of water disperse in air. Rain is caused by aggregation of
these minute particles, artificial rain can be done by throwing electrified sand or Agl from aeroplanes, colloidal
H2O particle present in cloud will get coagulated by these sand or Agl particles to form bigger water drops
causing rain.
 Stop bleeding from a cut : Blood is a colloidal solution containing a ñve charge colloidal particle
(Albuminoid), bleeding can be stopped by use of alum or FeCl3 solution. The addition of Al3+ or Fe3+ causes
coagulation of blood, so bleeding stops.
EMULSIONS :
Pair of immiscible liquid is called emulsion. Emulsion are unstable and some time they are separated into
two layers on keeping still, for the stabilising of an emulsion, a third component is added called emulsifying-
Agent form an interfacial film between D.P. and D.M.
Emulsion droplets are bigger than sol particles and can be seen under an ordinary microscope and sometimes
even with a magnifying glass.
Example : Milk is an emulsion in which liquid fat is D.P. and liquid water is D.M. and casein is emulsifying
agent.
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Surface Chemistry
 Demulsification : The separation of an emulsion into its constituent liquids is called demulsification.
Various techniques employed for this are freezing, boiling, centrifugation, electrostatic precipitation or chemical
methods which destroys the emulsifying agents.
Demulsification can be brought about by :
(i) Freezing
(ii) Heating
(iii) Centrifugal action (Separation of cream of milk done by centrifugation).
(iv) Removal of emulsifiers by adding a better solvent for them like alcohol, phenol etc, called demulsifiers.
Types of emulsions : Depending on the nature of the dispersed phase, the emulsions are classified as :
(a) Oil in water emulsions (b) Water in oil emulsions
(a) Oil in water emulsions (o/w) : This type of emulsions is formed when oil D.P. and water D.M.
Ex. :- Milk and vanishing cream are oil - in - water type emulsions.
(b) Water in oil emulsions (w/o) : This type of emulsions is formed when water is D.P. and oil is D.M.
Ex. : - Cold cream and cod liver oil.
[B] Applications of emulsions :

 Disinfactants like phenyl, dettol when mixed with water form emulsion.
 Digestion of fat in small intestine occurs easily due to emulsion.
 In metallurgical process the concentration of ore by froath floatation method is based upon emulsion.
 Milk is an emulsion of liquid fat in water in which casein emulsifying agent.
 Cleansing action of soap is due to formation of emulsions. Soaps and detergents emulsify the grease along
with the adhering dirt and carry them away in the wash water.
 For concentrating ores, the finely powdered ore is treated with an oil. Oil forms emulsion with the ore
particles. When air is bubbled into the mixture, emulsion containing the particles of the mineral are carried to
the surface.
MISCELLANEOUS SOLVED PROBLEMS (MSPs)

1. Which of the following is (are) lyophobic colloids ?
(A) Gold sol (B) As2 S3 sol (C) Starch sol (D) Fe(OH)3 sol
Sol. (ABD)
Gold sol, As2S3 and Fe(OH)3 are lyophobic colloid.
Therefore, (A, B, D) are correct options.
2. The presence of colloidal particles of dust in air imparts blue colour to the sky. This is due to
(A) Absorption of the light (B) Scattering of the light
(C) Reflection of the light (D) None of these
Sol. (B)
Due to scattering of the light.
Therefore, (B) is correct option.
3. The volume of nitrogen gas Um (measured at STP) required to cover a sample of silica gel with a mono-
molecular layer is 129 cm3 gñ1 of gel. Calculate the surface area per gram of the gel if each nitrogen molecule
occupies 16.2 E 10ñ20 m2.
Ans. 561.8 cm3
Sol. 22400 cm3 of N2 at STP contain = 6.022 E 1023 molecules
6.022  10 23  129
129 cm3 of N2 at STP will contain = = 3.468 E 1021 molecules
22400
Area occupied by a single molecule = 16.2 E 10ñ20 m2
 Area occupied by 3.468 E 1021 molecules of nitrogen = (16.2 E 10ñ20) E (3.468 E 1021) m2 = 561.8 m2.
AIPMTSCH - 21
Surface Chemistry
4. Which of the following has minimum gold number ?
(A) Potato starch (B) Gum arabic (C) Gelatin (D) Albumin
Sol. (C)
Gelatin has minimum gold number.
Therefore, (C) is correct option.
5. Which of the following are correctly matched ?
(A) Butter-gel (B) Milk-emulsion (C) Fog-aerosol (D) Dust-solid sol
Sol. (A, B, C) are correct matches.
6. Explain the adsorption of nitrogen on iron.
Sol. When nitrogen gas is brought in contact with iron at 83 K, it is physisorbed on iron surface as nitrogen
molecules, N2.As the temperature is increased the amount of nitrogen adsorbed decreases rapidly and at
room temperature, practically there is no adsorption of nitrogen on iron. At 773 K and above, nitrogen is
chemisorbed on the iron surface as nitrogen atoms.
7. How do size of particles of adsorbent, pressure of gas and prevailing temperature influence the extent of
adsorption of a gas on a solid ?
Sol. (a) Smaller the size of the particles of the adsorbent, greater is the surface area and hence greater is
the adsorption
(b) At constant temperature, adsorption first increases with increase of pressure and then attains
equilibrium.
(c) In physical adsorption, it decreases with increase of temperature but in chemisorption, first it
increases and then decreases.
8. How is adsorption of a gas is related to its critical temperature ?
Sol. Higher is the critical temperature of a gas, greater the van der Waalís forces of attraction and hence greater
is the adsorption.
9. Physical adsorption is essentially quite appreciable :

(A) at room temperature (B) at higher temperature
(C) at lower temperature (D) none of these
Sol. (C)
Rate of physical adsorption decreases with increase in temperature (exothermic process).
Therefore, (C) is correct option.
10. What type of colloidal sols are formed in the following ?
(i) Through cooled water, vapours of sulphur are passed.
(ii) White of an egg is mixed with water.
Sol. (i) Sulphur molecules associate together to form molecular sols.
(ii) Macromolecular sol because protein molecules present in the white of the egg are macromolecules & are
soluble in water.
11. What happens when persistent dialysis of a colloidal solution is carried out.
Sol. The stability of a colloidal sol is due to the presence of a small amount of the electrolyte. On persistent
dialysis, the electrolyte is completely removed. As a result, the colloidal sol becomes unstable and gets
coagulated.
AIPMTSCH - 22

Sheet 1 Surface Chemistry e

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Sheet 1 Surface Chemistry e

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Surface Chemistry

Difference between physical adsorption and chemical adsorption

(ii) CH3 COOCH3 ()   CH3 COOH(aq)

(ii) N2 (g)  3H2 (g)   2NH3 (g)

(iii) 4NH3 (g)  5O 2 (g)   4NO(g)  6H2O(g)

(iv) Vegetable oils ()  H2 (g)   Vegetable ghee (s).

(ii) 2KMnO 4  5 C OOH  3H2 SO 4  K 2 SO 4  MnSO 4 ( Auto catalyst)  8H2 O  10CO 2

(i) N 2  3H2    2NH 3

Vegetable Oil + H2 Cu( promoter

Platinised asbestos ( catalyst )

(iii) Rosunmund Reactions : RCOCl  H2  

 Factors Supporting Theory :

DP DM Type of colloid Examples

Solid Solid Solid Sol Some coloured glasses,

3. On the basis of charge of on particles

Aggregation of RCOOñ ions to form an ionic micelle.

(v) Acidic (negative colloids) and basic (positive colloids) dyes.

Sodium stearate (C17H35COOñ Na+) Hydrophobic tail

(c) (d) (e)

Preparation of lyophobic colloidal sols :

hydrochloric acid. Na4SiO4 + 4HCl  Si(OH)4 (sol) + 4NaCl.

(a) Electrical disintegration or Bredig's Arc method : This

Charge Colloidal particals of Fe (OH)3

True solution Colloidal solution

Example-5 Under what conditions is Tyndal effect observed ?

 Mechanical Properties :

(Fig. : A set up for electrophoresis.)

 Electric Double Layer Theory or Helm-holtz Electric double layer :

Example-7 Classify the following sols according to theirs charges :

 Coagulation/Flocculation : The presence of small amounts of appropriate electrolytes is necessary

coagulatin g power of electrolyt e A coagulatio n value B

[B] Applications of emulsions :

MISCELLANEOUS SOLVED PROBLEMS (MSPs)

9. Physical adsorption is essentially quite appreciable :

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